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I don't use XFCE myself but I found this thread that suggests that you can use the keyboard settings to set XF86AudioNext to exaile --next and XF86AudioPrev to exaile --prev. If that doesn't work out of the box, you may need to see what keycodes these media keys use with xev and put them in your .Xmodmap as described in the FAQ.

xev doesn't appear to see them or if it does I can't see them. Also - if I put them in xmodmap then what would happen with other apps that see the forward and back keys perfectly ok.
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23 93 26 35 19 57 3 89Jun 20 '12 at 11:29

@Elfy That other applications see them all right indicates to me that the so called keysym names are fine and you shouldn't need to map keycodes to them with xmodmap. I take it configuring the XFCE keyboard settings as described doesn't work either? You can also try evtest (it's in a package of the same name), see also this thread ask.fedoraproject.org/question/498/…
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ChristianJun 20 '12 at 12:39

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The same worked in Banshee for me, thanks! (banshee --next, --previous, --toggle-playback)
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culebrónJan 15 '13 at 14:17